CN105503670A - High-alkaline-value synthetic calcium alkyl benzene sulfonate nano detergent and preparation method thereof - Google Patents
High-alkaline-value synthetic calcium alkyl benzene sulfonate nano detergent and preparation method thereof Download PDFInfo
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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Abstract
The invention discloses high-alkaline-value synthetic calcium alkyl benzene sulfonate nano detergent and a preparation method thereof and belongs to the field of lubricating composite preparation. The high-alkaline-value synthetic calcium alkyl benzene sulfonate nano detergent is formed by compounding synthetic calcium alkyl benzene sulfonate, ball graupel crystal type calcium carbonate and base oil; the preparation method includes the steps of (1), preparation of a synthetic calcium alkyl benzene sulfonate solution; (2), preparation of the synthetic calcium alkyl benzene sulfonate nano detergent, (3) posttreatment and the like; the alkali content of a prepared product is higher than 400 mg KOH/g, the movement viscosity at the temperature of 100 DEG C is lower than 100 mm<2>/s, the product particle size is controlled within the range of 10-100 nm according to different preparation conditions, the particle size distribution is narrow, and the high-alkaline-value synthetic calcium alkyl benzene sulfonate nano detergent has the advantages of being high in alkaline value, low in viscosity, clear, stable and the like.
Description
Technical field
The invention belongs to lubricating composition preparation field, more particularly, synthesized calcium alkyl benzene sulfonate nanometer purification agent relating to a kind of high base number and preparation method thereof.
Background technology
Metal detergent is one of topmost additive in the internal combustion (IC) engine lubricating oil such as automobile, boats and ships.Its role is to: suppress and remove the high temperature deposition thing of piston face, reduce mechanical surface wearing and tearing; In and the acidic substance that produce of fuel oil incomplete combustion and oil product high temperature oxidation, prevent device from corrode, thus reach significantly prolongation oil product and service life of aeroengine object.Such purification agent is made up of tensio-active agent (sulfonate, alkylsalicylate, sulfuration alkyl salt etc.), carbonate (or borate) and thinning oil (synthetic oil, mineral oil) compound usually.Wherein, tensio-active agent is dispersion agent, with micelle form stable dispersion carbonate (or borate) particle, and the paint film existed in solubilising cylinder, colloid and carbon distribution; Carbonate (or borate) is neutralizing agent, with the necessary alkali of acidic by-products in providing; Thinning oil then as the Oil solvent of load micelle, micella, plays dispersion medium.At present, industrial extensive employing total basicnumber (TBN) evaluates the alkali content of purification agent product, with Equivalent Hydrogen potassium oxide milligram number (mgKOH/g) for unit, and adopts the relevant criterion such as ASTMD2896, GB/T0251 to measure.
Due to calcium sulfonate with high base number detergent feedstocks be easy to get, metallization process is simple and have excellent detergency, rust-preventing characteristic and thermostability concurrently, through the development of decades, it become in internal combustion (IC) engine lubricating oil be most widely used, one of detergent for lubricating oil that output is maximum.It not only may be used for allocating cylinder oil (the ZL96105367.4 lubricating oil composition with various property; CN1524936A ship use intermediate speed tubular diesel engine oil; ZL200410013726.5 energy-conserving and environment-protective lubricating oil; ZL200610042979.4 Sweet natural gas and gasoline dual purpose fuel engine lubricating oil) and additive (CN1293230A mono-kind controls the fuel oil additive of motor vehicle exhaust; CN1320682A oil dope; CN101100624A mono-kind lubricates oil additives and preparation method thereof), modification can also be converted into a complex calcium sulfonate grease (ZL02130820.9 high base number composite calcium sulfonate lubricating grease and preparation method thereof with the mechanical and colloid stability of extreme-pressure anti-wear, high-low temperature resistant, height further; ZL200310113489.5 complex lithium grease and preparation method thereof; ZL200510073101.2 composite calcium sulfonate grease lubricant and preparation method thereof).Therefore, obtained overbased calcium sulfonate detergents of how efficientlying is subject to extensive concern.
In general, calcium sulfonate with high base number purification agent mainly contains two kinds of preparation technologies: one-step synthesis process and multistep processes synthesis technique.One-step synthesis process is the method that employing carbonating obtains high-base-number detergent; The purification agent product of low alkali value during multistep processes synthesis technique is then first obtained by preliminary carbonating, then continue to add material obtains high-base-number detergent method by follow-up carbonating raising base number.As far back as nineteen sixty US Patent No. 2937991 disclose the method using sulfonate stable dispersion calcium carbonate in non-polar solvent.In more than 30 year subsequently, the scientists of developed country is by optimizing ingredient proportion, technical process, and preferred feedstock and promotor, disclose multiple calcium sulfonate with high base number class purification agent and preparation method thereof patent in succession (as US4810396; US4929373; US4995993 and US5011618).By comparison, domestic correlative study is started late, until eighties of last century just has the patent of the preparations and applicatio of Sulfonates purification agent open the nineties successively.Occur using mixed surfactant to prepare method (ZL03104813.7 low turbidity high base number mahogany acid calcium additive and preparation method thereof of sulfonate with high base number calcium salt purification agent; ZL97195134.9 overbased metal-containing detergents); Propose the method (preparation method of ZL200410037885.9 calcium sulfonate with high base number detergent for lubricating oil adopting higee technology to substitute traditional mechanical stirring autoclave preparation method acquisition Narrow diameter distribution calcium sulfonate detergents; CN101451087B mono-kind prepares the method for lubricant oil metal detergent).
It is as follows that typical calcium sulfonate detergents prepares scheme: use calcium oxide p-sulfonic acid to neutralize, obtain calcium sulphonate; Deposit in case in calcium sulphonate and other auxiliary material, with carbonic acid gas, carbonating is carried out to alkaline calcium salt, the calcium carbonate of generation is stably laid in the product under the parcel of calcium sulphonate tensio-active agent, thus obtain calcium sulfonate with high base number purification agent.Involved by current invention disclosed patent and in industrialized calcium sulfonate detergents product calcium carbonate granule is all there is (JournalofColloidandInterfaceScience, 1991,144:324-339) with unformed shape.Because the more unformed calcium carbonate of crystal form calcium carbonate has better extreme pressure, wear resistance (TribologyLetters, 2004,17:715-721; 2008,29:33-44).Therefore, with the purification agent product of crystal form nanoparticulate dispersed in oil phase if calcium carbonate can be obtained will be expected to improve the frictional behaviour of sulfonate detergent and reduce viscosity.But under common percarbonic acid condition, unformed calcium carbonate can be converted into calcite crystallization macrobead Precipitation, destroys the base number deposit of product, can not get the purification agent product (JournalofColloidandInterfaceScience of crystal type, 1991,144:324-339).
Chinese Patent Application No. is 200910011708.6, application publication date is the preparation method that the patent application document on October 7th, 2009 discloses overbased synthesized heavy alkyl benzene calcium sulfonate, add synthesized heavy alkyl benzene sulfonic acid in a reservoir, base oil, mixed solvent, alkaline earth metal halide, mixed-alkali calcified material carry out neutralization reaction 1 hour in 40 DEG C time, under normal pressure or negative pressure state, after reaction terminates, carry out desolventizing and low-volatile operation; When temperature reaches 135 DEG C, add super-cell to filter, normal salt product after filtration all returns throws back this there-necked flask, when temperature is down to 60 DEG C, add mixed solvent, mixed accelerators, mixed-alkali calcified material, control temperature of reaction between 30 ~ 40 DEG C, pass into carbonic acid gas with the flow velocity of 20g/ minute and carry out carbonation reaction, again carbonating material is pressed normal pressure desolvation, add filter aid and obtain product.But this patent exists reaction process to be made up of two-step approach, process complexity needs twice desolvation and twice filtration just can obtain final finished, and in the product obtained the crystal formation of calcium carbonate easily there is surface skining, have throw out, higher (the > 100mm of viscosity
2/ s) etc. phenomenon.
The present invention is by adopting rational preparation method and regulation and control material proportion, effectively control crystal formation and the particle size of the middle calcium carbonate of product, avoid the settlement issues generating calcite crystallization and produce, obtained by single stage method the calcium sulphonate lubricating oil nanometer purification agent that calcium carbonate is vaterite crystal type nano particle.Program material flow is simple, utilization ratio is high, and the stable clarification of product, has the advantage such as high base number, low viscosity concurrently, have broad application prospects.
Summary of the invention
1. the problem that will solve
All unformed shape for the calcium carbonate granule in existing calcium sulfonate detergents product, the problem such as there is extreme pressure property and wear resistance is not good, viscosity is high, synthesized calcium alkyl benzene sulfonate nanometer purification agent that the invention provides a kind of high base number and preparation method thereof, the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number of the present invention is made up of the calcium carbonate of synthesized calcium alkyl benzene sulfonate, vaterite crystal formation and base oil compound; Wherein, the alkali content of product is higher than 400mgKOH/g, and the kinematic viscosity under 100 DEG C of conditions is lower than 100mm
2/ s, different according to preparation condition, product particle size can be controlled within the scope of 10 ~ 100nm, narrow diameter distribution, has the advantages such as high base number, low viscosity, clear stable.
2. technical scheme
In order to solve the problem, the technical solution adopted in the present invention is as follows:
A preparation method for the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number, the steps include:
1) preparation of synthesized calcium alkyl benzene sulfonate solution: 50 ~ 100 parts of synthesis of alkyl Phenylsulfonic acids are dissolved in 50 ~ 350 parts of non-polar solvents, add 5 ~ 25 parts of low-carbon alcohol promotor, mixing, treat that system temperature is stabilized in 25 ~ 70 DEG C, add the calcium oxide of 8 ~ 15 parts, to keep under the condition of 20 ~ 50 DEG C more than stirring reaction half an hour;
2) preparation of synthesized calcium alkyl benzene sulfonate nanometer purification agent: to step 1) in synthesized calcium alkyl benzene sulfonate solution in add into 10 ~ 50 parts of low-carbon alcohol promotor, 0 ~ 5 part of secondary accelerator, 0.5 ~ 6 part of alkaline earth metal halide and 40 ~ 100 parts of mixed-alkali calcium salts, hierarchy of control temperature is 30 ~ 70 DEG C, passing into 35 ~ 100 parts of carbonic acid gas with constant flow rate to system makes mixture system cross alkalization, after reaction terminates, after adding 30 ~ 60 parts of base oil mixings, obtain the thick product of synthesized calcium alkyl benzene sulfonate nanometer purification agent;
3) aftertreatment: first adopt centrifugal, to filter or the method for press filtration is separated unreacted solid residue in thick product, the solvent in thick product, promotor and water is removed again by underpressure distillation, namely the high base number synthesized calcium alkyl benzene sulfonate nanometer purification agent that calcium carbonate is vaterite crystal formation is obtained, described underpressure distillation condition is vacuum tightness >0.090Mpa, and temperature is 50 ~ 70 DEG C;
The above number is mass fraction.
Preferably, step 1) described in the preparation method of synthesis of alkyl Phenylsulfonic acid be: by carbon number be 18 ~ 30 alhpa olefin and benzene generate alkylbenzene product through HF catalytic addition, then described synthesis of alkyl Phenylsulfonic acid is obtained through SO 3 sulfonated, its molecular weight is 400 ~ 600, the active matter content of sulfonic acid is 75 ~ 85%, and mineral acid content is 0 ~ 3%.
Preferably, the alkylbenzene product of generation is directly carried out fraction seperation in rectifying tower, and then obtain described synthesis of alkyl Phenylsulfonic acid through SO 3 sulfonated, its molecular weight is 450 ~ 500.
Preferably, choosing boiling range is that the cut of 290 DEG C ~ 400 DEG C carries out sulfonation reaction.
Preferably, step 1) described in non-polar solvent be short chain alkanes, substituted arene or both mixtures, described substituted arene is normal heptane, toluene, dimethylbenzene, 120# solvent oil or 180# solvent oil.
Preferably, step 1) described in low-carbon alcohol promotor be methyl alcohol, ethanol or ethylene glycol.
Preferably, step 2) described in secondary accelerator be quadrol or ammoniacal liquor; Step 2) described in alkaline earth metal halide be calcium chloride, magnesium chloride.
Preferably, step 2) described in mixed-alkali calcium salt be the mixture of calcium oxide and calcium hydroxide; Wherein, the mass ratio of calcium oxide and calcium hydroxide is 1:10 ~ 7:1.
Preferably, step 2) described in base oil be I class, II class or III class base oil in API's classification, comprise 100SN, 150SN, 200SN, 350SN.
Preferably, by step 3) in underpressure distillation change air distillation into, temperature is 120 ~ 150 DEG C.
A synthesized calcium alkyl benzene sulfonate nanometer purification agent for high base number, adopts the method described in above-mentioned any one to prepare.
3. beneficial effect
Compared to prior art, beneficial effect of the present invention is:
(1) the present invention adopts commercial synthesis alkyl benzene sulphonate (ABS) to be initiator, react under given conditions, obtain a kind of synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number first, calcium carbonate is wherein vaterite crystal formation, size tunable, utilization of materials is high, the stable clarification of product, have the advantage such as high base number, low viscosity concurrently, have broad application prospects;
(2) the present invention adopts rational preparation method and regulation and control material proportion, effectively control crystal formation and the particle size of calcium carbonate in product, avoid the settlement issues generating calcite crystallization and produce, and in the present invention the excessive product performance to vaterite-type nanometer purification agent of carbonic acid gas without obvious negative impact, add and have employed more compact one-step synthesis process, making this prepare scheme unformed purification agent product more in the past, to prepare scheme more simple, and utilization of materials is higher;
(3) the synthesized calcium alkyl benzene sulfonate nanometer purification agent product base number high (being greater than 400mgKOH/g) prepared of the present invention, viscosity is low (is less than 100mm at 100 DEG C
2/ s), be convenient to produce and transport, different according to preparation condition, product particle size can be controlled within the scope of 10 ~ 100nm, narrow diameter distribution, and use properties is good.
Accompanying drawing explanation
Fig. 1 is fourier infrared (FTIR) collection of illustrative plates of synthesized calcium alkyl benzene sulfonate nanometer purification agent in the embodiment of the present invention 1,877cm in figure
-1and 745cm
-1the characteristic peak at place shows that base number deposit calcium carbonate particles exists with vaterite crystal formation;
Fig. 2 is dynamic light scattering (DLS) collection of illustrative plates of synthesized calcium alkyl benzene sulfonate nanometer purification agent in the embodiment of the present invention 1;
Fig. 3 is transmission electron microscope (TEM) photo of synthesized calcium alkyl benzene sulfonate nanometer purification agent in the embodiment of the present invention 1;
Fig. 4 is fourier infrared (FTIR) collection of illustrative plates of unformed synthesized calcium alkyl benzene sulfonate purification agent in the embodiment of the present invention 3,862cm in figure
-1place's characteristic peak is the characteristic peak of unformed calcium carbonate.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
Low-carbon alcohol promotor in the present embodiment is methyl alcohol; Secondary accelerator is quadrol; Alkaline earth metal halide is magnesium chloride; Non-polar solvent is dimethylbenzene, and the step preparing the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number is:
(1) preparation of synthesized calcium alkyl benzene sulfonate solution: 230g synthesis of alkyl Phenylsulfonic acid is dissolved in 800mL dimethylbenzene, heated and stirred mixes, when system temperature rises to about 35 DEG C, add 30g methyl alcohol and 20g calcium oxide, promote heating bath temperature (temperature is designated as neutral temperature) herein, stirring reaction 45min under 40 DEG C of conditions, obtains synthesized calcium alkyl benzene sulfonate solution;
Synthesis of alkyl Phenylsulfonic acid production process in the present embodiment is: alhpa olefin carbochain being distributed as C18 ~ C30 directly carries out alkylated reaction so that HF is sour for catalyzer with purified petroleum benzin, generate alkylbenzene product, alkylbenzene product is carried out in rectifying tower de-benzene (removing unreacted benzene when rectification temperature is 100 ~ 250 DEG C), rectification process process, choose the cut that boiling range is 290 DEG C ~ 400 DEG C, described synthesis of alkyl Phenylsulfonic acid is obtained again through sulphur trioxide falling film sulfonation, reaction conditions is: vapour-liquid ratio 1.00 ~ 1.05:1, the concentration 2% of sulphur trioxide in reactant gases, temperature of reaction 40 DEG C, the molecular weight obtaining sulfonic acid is 450 ~ 500, active matter content is 75%, mineral acid content is 3%.
(2) preparation of vaterite crystal formation synthesized calcium alkyl benzene sulfonate nanometer purification agent: add 75g calcium oxide, 65g calcium hydroxide, 1g magnesium chloride, 0.5g quadrol and 40g methyl alcohol in above-mentioned synthesized calcium alkyl benzene sulfonate solution, stirring and evenly mixing, hierarchy of control temperature is 50 DEG C (being designated as carbonation temperature herein), passing into 83g carbonic acid gas with the speed of 300mL/min makes mixture system cross alkalization, after reaction terminates, remove heating bath, add the thick product obtaining synthesized calcium alkyl benzene sulfonate nanometer purification agent after 100g base oil (150SN) dilutes;
(3) aftertreatment: by thick product after press filtration removing solid residues, air distillation desolvation, promotor and water under 150 DEG C of conditions, can obtain the nanometer purification agent product that described calcium carbonate is vaterite crystal formation.
Output under the present embodiment condition is 571g, and be separated the solid residue 9g obtained, product total basicnumber (TBN) is: 405.3mgKOH/g, and the kinematic viscosity under 100 DEG C of conditions is 92.0mm
2/ s.Dynamic light scattering (DLS) measurement result (as shown in Figure 2) shows, the mean diameter of product is 34.4nm.Fourier infrared spectrum (as shown in Figure 1) shows, and the product prepared in the present embodiment exists 877cm
-1and 745cm
-1the charateristic avsorption band of vaterite crystal type calcium carbonate, show that the calcium carbonate deposit existed in product is the nano particle of vaterite crystal formation thus.Fig. 3 is transmission electron microscope (TEM) photo of the synthesized calcium alkyl benzene sulfonate nanometer purification agent prepared in the present embodiment, and as can be seen from the figure particle size range is within 100nm, and even particle size distribution.
Embodiment 2
The step of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number is prepared substantially with embodiment 1 in the present embodiment, difference is the intake changing carbonic acid gas, in the present embodiment, the intake of carbonic acid gas is 100g, and the product performance prepared are as shown in table 1.
Embodiment 3
The step of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number is prepared substantially with embodiment 1 in the present embodiment, difference is the intake changing carbonic acid gas, in the present embodiment, the intake of carbonic acid gas is 65g, and the product performance prepared are as shown in table 1.
Embodiment 4
The step of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number is prepared substantially with embodiment 1 in the present embodiment, difference is the intake changing carbonic acid gas, in the present embodiment, the intake of carbonic acid gas is 50g, and the product performance prepared are as shown in table 1.
Embodiment 3 and embodiment 4 are for comparing example, and time not enough for illustration of carbonic acid gas, utilization of materials low (residue showed increased), product viscosity are large, and in product, the calcium carbonate of stable dispersion is unformed.In embodiment 3, fourier infrared (FTIR) collection of illustrative plates of unformed synthesized calcium alkyl benzene sulfonate purification agent as shown in Figure 4,862cm in figure
-1place's characteristic peak is the characteristic peak of unformed calcium carbonate.
Carbon dioxide usage amount in table 1 embodiment 1-4 and product performance
Embodiment 5
Promotor in the present embodiment is ethylene glycol; Secondary accelerator is ammoniacal liquor; Alkaline earth metal halide is calcium chloride; Non-polar solvent is 120# solvent oil, and the step preparing the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number is:
(1) preparation of synthesized calcium alkyl benzene sulfonate solution: 230g synthesis of alkyl Phenylsulfonic acid is dissolved in 800mL120# solvent oil, heated and stirred mixes, when system temperature rises to about 35 DEG C, add 40g ethylene glycol and 20g calcium oxide, promote heating bath temperature, stirring reaction 45min under 40 DEG C of conditions, obtains synthesized calcium alkyl benzene sulfonate solution;
(2) preparation of vaterite crystal formation synthesized calcium alkyl benzene sulfonate nanometer purification agent: add 2g calcium chloride, 1.5g ammoniacal liquor in above-mentioned synthesized calcium alkyl benzene sulfonate solution, and 30g calcium oxide, 125g calcium hydroxide and 15g ethylene glycol (concrete charging capacity is in table 2), stirring and evenly mixing, under 40 DEG C of heating bath conditions, passing into 85g carbonic acid gas with the speed of 300mL/min to reaction system makes mixture system cross alkalization, after reaction terminates, remove heating bath, add the thick product obtaining synthesized calcium alkyl benzene sulfonate nanometer purification agent after 100g base oil (150SN) dilutes;
(3) aftertreatment: by thick product centrifugal treating 5min under 3000r/min condition, gained supernatant liquor is after decompress filter, in 60 DEG C, underpressure distillation desolvation, promotor and water under vacuum tightness 0.093 ~ 0.098Mpa condition, the nanometer purification agent product (product performance are in table 2) that described calcium carbonate is vaterite crystal formation can be obtained.
Synthesis of alkyl Phenylsulfonic acid production process in the present embodiment is: alhpa olefin carbochain being distributed as C18 ~ C30 directly carries out alkylated reaction so that HF is sour for catalyzer with purified petroleum benzin, generate alkylbenzene product, alkylbenzene product is carried out in rectifying tower de-benzene (removing unreacted benzene when rectification temperature is 100 ~ 250 DEG C), rectification process process, choose the cut that boiling range is 290 DEG C ~ 400 DEG C, described synthesis of alkyl Phenylsulfonic acid is obtained again through sulphur trioxide falling film sulfonation, reaction conditions is: vapour-liquid ratio 1.00 ~ 1.05:1, reaction gas dense (concentration of sulphur trioxide) controls 6%, temperature of reaction controls at 60 DEG C, the molecular weight obtaining sulfonic acid is 450 ~ 500, active matter content is 85%, mineral acid content is 0.1%.
Embodiment 6
Prepare the step of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number in the present embodiment substantially with embodiment 5, difference be change ethylene glycol, calcium oxide, calcium hydroxide charging capacity, concrete charging capacity and the product performance prepared as shown in table 2.
Embodiment 7
Prepare the step of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number in the present embodiment substantially with embodiment 5, difference be change ethylene glycol, calcium oxide, calcium hydroxide charging capacity, concrete charging capacity and the product performance prepared as shown in table 2.
The charging capacity of the ethylene glycol in table 2 embodiment 5-7, calcium oxide, calcium hydroxide and the performance of product
By the result in embodiment 5-7 and table 2, the charge ratio by changing promotor ethylene glycol, calcium oxide and calcium hydroxide is described, in technical process of the present invention, the calcium sulphonate sample that calcium carbonate crystal formation is vaterite-type, total basicnumber is greater than 400mgKOH/g can be obtained.
Embodiment 8
Promotor in the present embodiment is ethanol; Secondary accelerator is quadrol; Alkaline earth metal halide is calcium chloride; Non-polar solvent is normal heptane, and the step preparing the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number is:
(1) preparation of synthesized calcium alkyl benzene sulfonate solution: 230g synthesis of alkyl Phenylsulfonic acid is dissolved in 800mL normal heptane, heated and stirred mixes, when system temperature rises to about 35 DEG C, add 30g ethanol and 20g calcium oxide, then control heating bath temperature (temperature is designated as neutral temperature) stirring reaction 45min at 30 DEG C herein;
(2) preparation of vaterite crystal formation synthesized calcium alkyl benzene sulfonate nanometer purification agent: add 30g calcium oxide to above-mentioned synthesized calcium alkyl benzene sulfonate solution, 125g calcium hydroxide, 3g calcium chloride, 1g quadrol, and 60g ethanol (see table 3), stirring and evenly mixing, (carbonation temperature is designated as herein) under 60 DEG C of heating bath conditions, passing into 85g carbonic acid gas with the speed of 300mL/min to reaction system makes mixture system cross alkalization, after reaction terminates, remove heating bath, add the thick product obtaining synthesized calcium alkyl benzene sulfonate nanometer purification agent after 100g base oil (150SN) dilutes,
(3) aftertreatment: thick product is after press filtration removing solid residues, air distillation desolvation, promotor and water under 150 DEG C of conditions, can obtain the nanometer purification agent product (product performance are in table 3) that described calcium carbonate is vaterite crystal formation.
Synthesis of alkyl Phenylsulfonic acid production process in the present embodiment is: alhpa olefin carbochain being distributed as C18 ~ C30 directly carries out alkylated reaction so that HF is sour for catalyzer with purified petroleum benzin, generate alkylbenzene product, alkylbenzene product is carried out in rectifying tower de-benzene (removing unreacted benzene when rectification temperature is 100 ~ 250 DEG C), rectification process process, choose the cut that boiling range is 290 DEG C ~ 400 DEG C, described synthesis of alkyl Phenylsulfonic acid is obtained again through sulphur trioxide falling film sulfonation, reaction conditions is: vapour-liquid ratio 1.00 ~ 1.05:1, reaction gas is dense to be controlled 4%, temperature of reaction controls at 50 DEG C, the molecular weight obtaining sulfonic acid is 450 ~ 500, active matter content is 80%, mineral acid content is 1%.
Embodiment 9
Prepare the step of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number in the present embodiment substantially with embodiment 8, difference changes the dosage of ethanol and neutral temperature and carbonation temperature, actual conditions and the product performance prepared as shown in table 3.
Embodiment 10
Prepare the step of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number in the present embodiment substantially with embodiment 8, difference changes the dosage of ethanol and neutral temperature and carbonation temperature, actual conditions and the product performance prepared as shown in table 3.
The charging capacity of the ethanol of table 3 embodiment 8-10, calcium oxide, calcium hydroxide and product performance
By the result in embodiment 8-10 and table 3, the charge ratio by changing promotor ethanol, calcium oxide and calcium hydroxide is described, in technical process of the present invention, the calcium sulphonate sample that calcium carbonate crystal formation is vaterite-type, total basicnumber is greater than 400mgKOH/g can be obtained.
Embodiment 11
Prepared by ultra-low viscosity vaterite crystal type nano purification agent
(1) preparation of synthesized calcium alkyl benzene sulfonate solution: 180g synthesis of alkyl Phenylsulfonic acid is dissolved in 800mL dimethylbenzene, heated and stirred mixes, and adds 30g methyl alcohol, 15g calcium oxide, stirring reaction 45min under 30 DEG C of oil baths;
(2) preparation of vaterite crystal formation synthesized calcium alkyl benzene sulfonate nanometer purification agent: add 75g calcium oxide, 65g calcium hydroxide, 4g calcium chloride, 1g ammoniacal liquor and 40g methyl alcohol, stirring and evenly mixing in above-mentioned synthesized calcium alkyl benzene sulfonate solution.Under 50 DEG C of heating bath conditions, passing into 85g carbonic acid gas with the speed of 300mL/min to reaction system makes mixture system cross alkalization, after reaction terminates, remove heating bath, add the thick product obtaining synthesized calcium alkyl benzene sulfonate nanometer purification agent after 160g base oil (150SN) dilutes;
(3) aftertreatment: thick product is after press filtration removing solid residues, and air distillation desolvation, promotor and water under 150 DEG C of conditions, can obtain the nanometer purification agent product that described calcium carbonate is vaterite crystal formation.
Output under the present embodiment condition is 572g, and be separated the solid residue 7g obtained, product total basicnumber is 394.4mgKOH/g, and the kinematic viscosity under 100 DEG C of conditions is 32.5mm
2/ s.Dynamic light scattering (DLS) measurement result shows, the particle dia of product is 39.9nm.Infrared spectra (FTIR) analysis shows, product exists 877cm
-1and 745cm
-1vaterite crystalline characteristics absorption peak, show that in product, calcium carbonate is vaterite crystal formation.
Claims (10)
1. a preparation method for the synthesized calcium alkyl benzene sulfonate nanometer purification agent of high base number, the steps include:
1) preparation of synthesized calcium alkyl benzene sulfonate solution: 50 ~ 100 parts of synthesis of alkyl Phenylsulfonic acids are dissolved in 50 ~ 350 parts of non-polar solvents, add 5 ~ 25 parts of low-carbon alcohol promotor, mixing, treat that system temperature is stabilized in 25 ~ 70 DEG C, add the calcium oxide of 8 ~ 15 parts, under the condition of 20 ~ 50 DEG C more than stirring reaction half an hour;
2) preparation of synthesized calcium alkyl benzene sulfonate nanometer purification agent: to step 1) in synthesized calcium alkyl benzene sulfonate solution in add into 10 ~ 50 parts of low-carbon alcohol promotor, 0 ~ 5 part of secondary accelerator, 0.5 ~ 6 part of alkaline earth metal halide and 40 ~ 100 parts of mixed-alkali calcium salts, hierarchy of control temperature is 30 ~ 70 DEG C, passing into 35 ~ 100 parts of carbonic acid gas with constant flow rate to system makes mixture system cross alkalization, after reaction terminates, after adding 30 ~ 60 parts of base oil mixings, obtain the thick product of synthesized calcium alkyl benzene sulfonate nanometer purification agent;
3) aftertreatment: first adopt centrifugal, to filter or the method for press filtration is separated unreacted solid residue in thick product, the solvent in thick product, promotor and water is removed again by underpressure distillation, namely the high base number synthesized calcium alkyl benzene sulfonate nanometer purification agent that calcium carbonate is vaterite crystal formation is obtained, described underpressure distillation condition is vacuum tightness >0.090Mpa, and temperature is 50 ~ 70 DEG C;
The above number is mass fraction.
2. the preparation method of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of a kind of high base number according to claim 1, it is characterized in that: step 1) described in the preparation method of synthesis of alkyl Phenylsulfonic acid be: by carbon number be 18 ~ 30 alhpa olefin and benzene generate alkylbenzene product through HF catalytic addition, then described synthesis of alkyl Phenylsulfonic acid is obtained through SO 3 sulfonated, its molecular weight is 400 ~ 600, the active matter content of sulfonic acid is 75 ~ 85%, and mineral acid content is 0 ~ 3%.
3. the preparation method of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of a kind of high base number according to claim 2, it is characterized in that: the alkylbenzene product of generation is carried out fraction seperation in rectifying tower, and then obtaining described synthesis of alkyl Phenylsulfonic acid through SO 3 sulfonated, its molecular weight is 450 ~ 500.
4. the preparation method of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of a kind of high base number according to claim 3, is characterized in that: choosing boiling range is that the cut of 290 DEG C ~ 400 DEG C carries out sulfonation reaction.
5. the preparation method of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of a kind of high base number according to claim 1, it is characterized in that: step 1) described in non-polar solvent be short chain alkanes, substituted arene or both mixtures, described substituted arene is normal heptane, toluene, dimethylbenzene, 120# solvent oil or 180# solvent oil.
6. the preparation method of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of a kind of high base number according to claim 1, is characterized in that: step 1) described in low-carbon alcohol promotor be methyl alcohol, ethanol or ethylene glycol.
7., according to the preparation method of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of a kind of high base number described in claim 2 or 5, it is characterized in that: step 2) described in secondary accelerator be quadrol or ammoniacal liquor; Step 2) described in alkaline earth metal halide be calcium chloride, magnesium chloride; Step 2) described in mixed-alkali calcium salt be the mixture of calcium oxide and calcium hydroxide; Wherein, the mass ratio of calcium oxide and calcium hydroxide is 1:10 ~ 7:1.
8. the preparation method of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of a kind of high base number according to claim 1, it is characterized in that: step 2) described in base oil be API classification in I class, II class or III class base oil, comprise 100SN, 150SN, 200SN, 350SN.
9. the preparation method of the synthesized calcium alkyl benzene sulfonate nanometer purification agent of a kind of high base number according to claim 1, is characterized in that: by step 3) in underpressure distillation change air distillation into, temperature is 120 ~ 150 DEG C.
10. a synthesized calcium alkyl benzene sulfonate nanometer purification agent for high base number, is characterized in that: adopt the method in claim 1-9 described in any one to prepare.
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